CN103723735A - Process for hydrogenating silicon tetrachloride to trichlorosilane - Google Patents
Process for hydrogenating silicon tetrachloride to trichlorosilane Download PDFInfo
- Publication number
- CN103723735A CN103723735A CN201310474431.7A CN201310474431A CN103723735A CN 103723735 A CN103723735 A CN 103723735A CN 201310474431 A CN201310474431 A CN 201310474431A CN 103723735 A CN103723735 A CN 103723735A
- Authority
- CN
- China
- Prior art keywords
- boron
- hydrogen
- heating unit
- silicon tetrachloride
- stc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000005049 silicon tetrachloride Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 39
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 title claims description 40
- 239000005052 trichlorosilane Substances 0.000 title claims description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 56
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000007789 gas Substances 0.000 claims abstract description 28
- 150000001639 boron compounds Chemical class 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 15
- 239000010439 graphite Substances 0.000 claims abstract description 15
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 12
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000085 borane Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims description 36
- 238000005984 hydrogenation reaction Methods 0.000 claims description 17
- 230000000977 initiatory effect Effects 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 239000000376 reactant Substances 0.000 abstract description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 23
- 229910052796 boron Inorganic materials 0.000 description 23
- 229910052710 silicon Inorganic materials 0.000 description 20
- 239000010703 silicon Substances 0.000 description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000000151 deposition Methods 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- 230000001186 cumulative effect Effects 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 7
- 239000005046 Chlorosilane Substances 0.000 description 6
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 6
- 229910010271 silicon carbide Inorganic materials 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000002912 waste gas Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- -1 diborane Chemical compound 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical class Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/02—Boron; Borides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention provides a process for hydrogenating silicon tetrachloride in a reactor, in which reactant gas containing hydrogen and silicon tetrachloride is heated to a temperature of greater than 900 DEG C. at a pressure between 4 and 15 bar, first by means of at least one heat exchanger made from graphite and then by means of at least one heating element made from SiC-coated graphite, the temperature of the heating elements being between 1150 DEG C. and 1250 DEG C., wherein the reactant gas includes at least one boron compound selected from the group consisting of diborane, higher boranes, boron-halogen compounds and boron-silyl compounds, the sum of the concentrations of all boron compounds being greater than 1 ppmv based on the reactant gas stream.
Description
Technical field
The present invention relates to silicon tetrachloride (STC) hydrogenation to become the method for trichlorosilane (TCS).
Background technology
Trichlorosilane is normally made by metalluragical silicon and hydrogenchloride in fluidized bed process.In order to obtain highly purified trichlorosilane, distill subsequently.At this, also produce silicon tetrachloride as by product.
When deposit spathic silicon, produce the silicon tetrachloride of most amounts.Polysilicon for example obtains by Siemens Method.At this, silicon deposits in reactor on the thin rod of heating.In the situation that there is hydrogen, the process gas that is used as silicon containing component is halosilanes, as trichlorosilane.When trichlorosilane reaction (disproportionation) generates the silicon of deposition, produce a large amount of silicon tetrachlorides.
By silicon tetrachloride for example by the silicon-dioxide that at high temperature can produce high dispersing in combustion chamber that reacts with hydrogen and oxygen.
But the interesting application economically of silicon tetrachloride is that hydrogenation becomes trichlorosilane.This is to carry out with hydrogen generation trichlorosilane and reacting of hydrogenchloride by silicon tetrachloride.Can generate trichlorosilane by the silicon tetrachloride as by-product producing thus between depositional stage, and this trichlorosilane is sent into again to deposition process, to produce elemental silicon.
Utilize process that hydrogen becomes trichlorosilane by hydrogenation of silicon tetrachloride normally in reactor at high temperature, at least 600 ℃, (pyrolytic conversion) carried out at least 850 ℃ ideally.
In order to reach described high temperature, the heating unit that need to be made by extremely heat-resisting material.Use carbonaceous material, for example graphite for this reason.As shown below, be debatable especially when utilizing hydrogeneous gas that the heating unit of carbon containing heats to carry out pyroprocessing, this is noticed in the prior art.
Except the problem of having addressed in the prior art, also can produce new problem, this problem particularly in the situation that the long time of reactor running and comparing occur.Therefore, can observe, As time goes on and continuously the resistance of heating unit raise.Because the desired electric power remaining unchanged should be provided, this resistance rising phenomenon has proposed extra technical requirements for the supply of electric power of heating unit.Therefore, even more advantageously, avoid or at least reduce the problem of heater element resistance rising.
US 4,536,642 A disclose a kind of equipment for pyroprocessing gas, and it consists of lagging casing, and this lagging casing has gas inlet and pneumatic outlet and is arranged on the inertia resistance heating element that direct circulating current heats that passes through between these openings.This heating unit is comprised of graphite.Extraly, the heat exchange unit that the gas exhausting device by not heating can be formed is fitted in this shell, because this reason for save energy of initial reactant that heats this reaction by the hot waste gas of this reactor is significant.The waste gas of heat comprises product and unreacted initial reactant.
This kind equipment is also particularly suitable for STC hydrogenation to become TCS.
Because require high thermostability, heating unit used is made by suitable material.For the reason of thermostability, graphite is specially suitable in theory, but contained carbon reacts and generates methane with the hydrogen of inflow at this temperature.
For example US 7,442,824 B2 suggestions, before making chlorosilane hydrogenation to the surface of heating unit in original position coating silicon carbide, reduce thus the methanation phenomenon of these assemblies.The step of this coating silicon carbide is carried out at the temperature of at least 1000 ℃.
However, still can there is methanation phenomenon in the graphite member through applying, and still always observe corrosion phenomenon related to this.H
2/ STC mixture generates other carbon compounds with the carbon comprising in heating unit can cause the textural defect in heating unit as also reacting of METHYL TRICHLORO SILANE and dimethyl dichlorosilane (DMCS), causes reactor fault, thereby shortens the life-span of reactor.
Because defective parts must be changed, because again buy required replacement parts and installation costs, this means extra quite high financial cost.
Especially on the heating unit directly contacting with STC with hydrogen, there is methanation phenomenon.
This is owing to producing more spall and broken thing and more obvious, and they drop on reactor bottom, for example causes ground connection, and cause thus heating unit fault at this in worst situation.
US 7,998, and 428 B2 disclose a kind of for initial action gas silicon tetrachloride and hydrogen are sent in reaction compartment to obtain the equipment of the product gas that comprises trichlorosilane and hydrogenchloride.This equipment is arranged on reaction compartment and heating unit in a container of sending into argon gas.Therefore, this reaction compartment and heating unit are arranged in the outside vessel that argon gas is housed under pressure.Therefore can avoid process gas to leak.Therefore can also realize heating unit not by the effect of hydrogen attack.
But shortcoming is, reaction compartment and heating unit are separated from one another, therefore need the temperature that heating unit is higher.This can damage electricwire conduit again.
In addition, heating space must have the insulation stronger to outside, the diameter of this meeting increasing device.
Need equally intricately to regulate pressure, therefore cannot be by hydrogen injection heating space.
DE 199 49 936 A1 have described a kind of method for the assembly of being made by graphite material and carbon material is kept when nitrogen atmosphere is used at the temperature higher than 400 ℃ at it, it is characterized in that, depend on that temperature and pressure sneaks into this nitrogen atmosphere with the ratio of stoichiometric balance between hydrogen and methane by methane.
Although introducing on the operating principle of methane extraly, this is suitable for protecting heating unit and heat exchanger; but in the process that STC hydrogenation is become to TCS, can cause forming more unexpected reaction product (methyl chlorosilane and hydro carbons), this causes the quite complicated still-process carrying out in order to isolate from chlorosilane.
US 2011/0110839 A1 relates to a kind of passing through by STC, metalluragical silicon and H
2hydrochlorinate effect prepare the method for TCS, wherein in a plurality of steps pack processing containing TCS, STC, H
2, Si and metal-salt product gas mixture, so that TCS is separated with other compositions especially solids component with STC.
Gas stream from heating unit to reactor can comprise hydrogenchloride, dichlorosilane, TCS, STC and impurity, as phosphorus chloride, phosphorus trichloride and boron trichloride, diborane, methane, phosphine and water.The temperature of this gas is approximately 580 ℃, and pressure is 22.5bar.
Under this reaction conditions, not there is not or only occur unconspicuous methanation in heating unit.Only under higher temperature and lower pressure, just can there is this effect.But whole method is also not suitable for the very pure STC hydrochlorinate for example being reclaimed by deposition to become TCS, because this relates to sizable evitable cost and inconvenience for purifying.
US 6,932, and 954 B2 disclose a kind of method, comprise by TCS and H
2deposit spathic silicon, by making the waste gas of auto-deposition to contact and prepare TCS with rough silicon, wherein silicon reacts with HCl contained in waste gas, and the waste gas of the step from preparation TCS is processed to isolate TCS, thereby subsequently TCS is added into deposition process.In the resistates from treating processes, comprise STC, and used H
2hydrogenation becomes TCS.Hydrogen can be isolated from chlorosilane by cooling.Isolated hydrogen can comprise a large amount of boron compounds.This boron compound can be removed by hydrogen is contacted with the material that comprises one of following functional group: – NR
2(R representative has the alkyl), – SO of 1 to 10 C atom
3h, – COOH Huo – OH.Boron compound in chlorosilane (halogenation boron) can be removed by distillation, to reduce the boron content in silicon and to obtain thus the silicon with required qualitative characteristic.
Be similar to US 2011/0110839 A1, TCS forms step and carries out as hydrochlorinate effect by rough silicon.Under this reaction conditions, not there is not or only occur unconspicuous methanation in heating unit.Through heating unit, enter TCS and form the streams (H in step
2and STC) not by the contaminating impurity such as boron.
The shortcoming of the method is, initial unpolluted hydrogen again must intricately purifying after TCS forms step, and then it just can be for depositing.
US 2009/060819 A1 discloses a kind of method, wherein for example by multiple deposition and distillation, byproduct stream is processed in the following way, especially the STC of the pollution that comprises STC and other higher-boiling compounds is carried out to purifying, isolate thus higher-boiling compound, and its hydrogenation is become to TCS.The STC of this pollution is in purifying TCS(distillation, absorption) time obtains.
Because the synthetic starting material of TCS are metalluragical silicons, so by product also comprises impurity, as carbon compound, boron compound and phosphorus compound.US 2009/060819 A1 has imagined pure especially STC(HP-STC for STC hydrogenization), it comes from separated by product chlorination and purifying subsequently.For the hydrogen of STC hydrogenization, stemming from the source identical with source for depositing, is therefore pure especially, because otherwise impurity in silicon can damage the quality of product.
The method cannot solve in STC hydrogenization the problem that the form with the methanation of heating unit produces.
US 3,455, and 745 A relate to object is applied with silication four boron (TBS), and it is known has extremely strong tolerance for oxygenizement.In the situation that the object of being made by silicon, hydrogen and boron trichloride or diborane are delivered to the object that is arranged in reactor, on this object, form thus TBS layer.The object of being made by boron also can apply with TBS: for example add STC or other halosilanes and hydrogen (or TCS and H for this reason
2).Under the both of these case being combined as requested, by gas, be that hydrogen, STC/TCS and boron trichloride/diborane are heated to the temperature of 1000 to 1200 ℃.The object being not comprised of silicon or boron also can apply with TBS.First with boron or with silicon, apply this object for this reason.This is to be undertaken by the thermolysis of boron compound or silicon compound.For example, by applying silicon layer with hydrogen reduction TCS on the rod being formed by graphite.Can utilize hydrogen and boron trichloride or diborane on this silicon layer, to apply TBS layer.
According to US 3,455,745 A for applying with TBS, need to arrange at least one silicon layer on the surface of object to be coated.Therefore, in the situation that the object being comprised of graphite, first by trichlorosilane, the thermolysis at the temperature of 1150 ℃ applies, and then starts to apply with TBS.
But find, the heating unit applying in this way has in the tendency over time of viewed resistance before, and this can cause proposing higher requirement for supply of electric power, and this can cause very adverse influence to the economy of the method again.
Summary of the invention
The object of the present invention is to provide the method that STC hydrogenation is become to TCS, wherein heating unit used does not demonstrate the resistance change tendency significantly raising in time, but has avoided the shortcoming of prior art simultaneously.
This object is by for make the method for hydrogenation of silicon tetrachloride realize at reactor, wherein first utilize at least one heat exchanger of being made by graphite and utilize subsequently at least one heating unit of being made by the graphite applying with SiC that the initial action gas that comprises hydrogen and silicon tetrachloride is heated to be greater than the temperature of 900 ℃ under 4 to 15bar pressure, temperature at this heating unit is 1150 ℃ to 1250 ℃, it is characterized in that, described initial action gas comprises at least one and is selected from the boron compound in following group: diborane, more senior borine, boron-halogen compounds and boron-silyl compound, wherein based on initial action gas stream, the concentration sum of all boron compounds is greater than 1ppmv.
The preferred embodiment of described method is asked for protection in the dependent claims.
By the method according to this invention, unexpectedly produce two kinds of effects, although the method that there is no understand completely, but reproducible.
On the one hand, significantly reduce the heating unit fault that the spall due to heating unit causes and the reactor fault occurring thus.On the other hand, reduce the phenomenon of the electrical resistance time rising of heating unit simultaneously, in the long playing situation of reactor, needn't propose higher requirement for supply of electric power thus.This has significantly reduced cost of investment.
As be known in the art, object can adopt appropriate means to apply with TBS in principle, improves thus the tolerance for oxygenizement.In the experiment of being implemented by the present inventor, on heating unit, can't detect TBS layer.
Even if suppose to be similar to US 3,455,745 A form TBS layer, still cannot explain heating unit resistance characteristic in time.In experiment, opening and closing boron source clearly illustrates that in time, compares with the situation of closing subsequently boron source, and tendency is obviously milder over time in the situation that opening boron source, can to observe resistance.This effect has very good reproducibility, and the in the situation that of opening and closing boron source repeatedly, produces with the mild and resistance change tendency resistance change tendency that strictly monotone raises in time sharply alternately.Therefore, by forming possibly the known TBS layer that there is weak oxidizability and be therefore difficult to remove, in any case cannot explain the phenomenon that the resistance of generation sharply raises immediately after closing boron source.
In the situation that making STC hydrogenation, common excessive use hydrogen (H2:STC=2:1-10:1), and after isolating condensable chlorosilane and HCl again in circulation using it as initial reactant for STC hydrogenation.
Except the hydrogen from recirculation step, can also use from the pure hydrogen of steam reformer or from the pure hydrogen of multiple deposition (poly deposition).
The hydrogen of these kinds has high purity, for example the methane of <10ppmv or the boron compound of <100ppta.
In the recirculation step of the hydrogen from STC hydrogenation, methane and other hydro carbons enrichments (up to 5000ppmv), but do not observe the enrichment of boron compound.
Find different types of H
2middle different methane content (<10ppmv or <5000ppmv) does not obviously have measurable effect for the methanation of graphite components and heating unit.For the infringement of assembly in comparable degree.The resistance of heating unit over time tendency demonstrates similar variation tendency for different types of hydrogen.
This shows, even at CH
4in the situation of content high (but lower than equilibrium composition), cannot on assembly, form enough densification or interior poly-SiC layer, this layer protects assembly can be further by hydrogen attack, or changes enduringly the variation tendency of resistance.
But have been surprisingly found that, even if add a small amount of diborane (B of about 1ppmv
2h
6) to hydrogen, still obtain the more favourable variation tendency of the resistance-time curve of heating unit.This realizes obviously less infringement of heating unit simultaneously.
For STC hydrogenation being become to the traditional method of TCS, by using pure initial reactant (STC and from the H of multiple deposition
2or STC and from the H of recirculation step
2) and avoid introducing boron.STC or from the H of multiple deposition
2there is inherently low foreign matter content, because for example boron compound dilution on polysilicon.
Think at present, via the initial reactant of STC hydrogenation, introduce extraly boron and cause the boron concentration in target product to raise, and cause thus obviously higher complicacy to carry out the purifying distillation of product.
Yet have been surprisingly found that completely, the boron of sending into is extraly enrichment, also not enrichment in treated hydrogen in the reaction product of liquid (condensation) neither.
This can also be confirmed by temporary close boron source, because the positive effect for the resistance change tendency of heating unit reduces after the short period of time.
At boron in this system enrichment in the situation that, the more permanent effect of having to expect to continue.
Therefore in this experiment, the boron of interpolation must be for example absorbs in reactor by introducing in formed SiC layer extraly, or together with passing through H
2the hydrogenchloride that recirculation step produces is discharged together.To this, cannot carry out the quantam of proof.On heating unit, form SiC layer, but do not form silication four boron layers.
For according to method described in the invention process, boron compound can be added into the logistics of hydrogen initial action.
This for example can be by sending into the B of definite amount
2h
6or other gaseous boron compound and realizing.
Another preferred embodiment of the present invention is, boron compound is sent in the logistics of STC initial action.
Preferably will under selected processing condition (temperature and pressure), be in a liquid state or soluble boron compound is sent in STC stream, so it evaporates together with chlorosilane.
The boron compound adding is more easily to volatilize or more difficult volatilization with respect to STC, and this is inessential for successful implementation the present invention.
Boron-halogen compounds and B-silyl compound and more senior borine decompose at the temperature higher than 600 ℃, and the generation effect identical with diborane.
By measuring resistance change, can make the degree of damage of heating unit quantize.The ratio resistance that makes conventionally to contain the heating unit of graphite due to methanation reaction raises significantly, and also makes thus the total electrical resistance of heating unit raise.The heating unit decoration form with the independent resistance that can be calculated by electric current and voltage of independent adjustable/controllable heating unit and these heating units is proved to be particularly advantageous at this.
This decoration form allows common a plurality of independent heater element resistances to calculate and observe.
By observing these resistance, can indirectly observe due to the infringement of methanation reaction to heating unit.
Accompanying drawing explanation
Fig. 1 to 3 is depicted as experimental result.
Embodiment
Embodiment
These embodiment, according to US 4,536, implement in the equipment of 642 A.Gaseous mixture in the initial action logistics that use is comprised of 33 % by mole of silicon tetrachlorides and 67 % by mole of hydrogen.The temperature in of initial action gas stream is approximately 175 ℃.Regulate pressure to 6bar, regulate the temperature to 1 of the gas in space reactor, 000 ℃.
In experiment, pointedly boron compound diborane is added into hydrogen by metering, the while is with respect to the variation of reference measurement of resistance resistance.
Fig. 1 has schematically shown result.X-coordinate is depicted as time t, and ordinate zou is depicted as the relative resistance R/R in per-cent
0.By moment t
0rise, for situation B, C and D, by metering, add diborane extraly.Situation A is regarded as with reference to situation (prior art), and it comprises and as impurity, in cumulative volume stream, is less than the concentration of boron of 0.5ppmv.The diborane of 1ppmv in experiment B(cumulative volume stream), the diborane of 4ppmv in experiment C(cumulative volume stream) and experiment D(cumulative volume flow in the diborane of 5ppmv) in can unexpectedly observe, once add diborane by metering extraly, the change of electrical resistance time reduces.This effect can be observed in situation B, but obvious especially in situation D.
Unexpectedly observe, once the degree of use boron pollution in cumulative volume stream is greater than the hydrogen of 1ppmv, reduced the degree of electrical resistance time rising.
In another experiment, repeatedly start and stop to add by metering the process of diborane (based on cumulative volume stream 4ppmv).Result schematically shows in Fig. 2.X-coordinate is depicted as time t, and ordinate zou is depicted as relative resistance R/R
0.In time range E, do not carry out adding by metering the process of diborane.As expect, resistance change tendency strictly monotone raises.From time range F, by metering, add diborane, and with by metering adding procedure, almost synchronously reduced the gradient of resistance change tendency.In time range G, stop adding by metering, this causes resistance to raise as previously mentioned again.At this, do not observe time of lag.This effect occurs immediately.If again open by metering adding procedure (scope H), the gradient of resistance almost reduces immediately again.
Between adding by metering and adding not according to metering, switch, cause significantly this system to be reacted immediately with the form of the different gradients of the relative resistance of heating unit.For example, if extra layer (TBS) is the reason that causes resistance change tendency to change, must measure obvious time of lag, in this time of lag, form or eliminate corresponding layer.
In another experiment, the in the situation that of equating (based on cumulative volume stream 4ppmv) in boron concentration, the temperature on heating unit surface raises in time.
The result of this experiment is schematically shown in Fig. 3.
X-coordinate is depicted as time t, and the ordinate zou in left side is depicted as the relative resistance R/R in per-cent
0.Over time, it can utilize pyrometer to measure to the temperature that the ordinate zou on right side is depicted as heating unit.Can determine, the gradient of resistance curve (dotted line) has minimum value in the scope of 1150 ℃ to 1250 ℃.
Claims (7)
1. for make the method for hydrogenation of silicon tetrachloride at reactor, wherein first utilize at least one heat exchanger of being made by graphite and utilize subsequently at least one heating unit of being made by the graphite applying with SiC that the initial action gas that comprises hydrogen and silicon tetrachloride is heated to be greater than the temperature of 900 ℃ under 4 to 15bar pressure, temperature at this heating unit is 1150 ℃ to 1250 ℃, it is characterized in that, described initial action gas comprises at least one and is selected from the boron compound in following group: diborane, more senior borine, boron-halogen compounds and boron-silyl compound, wherein based on initial action gas stream, the concentration sum of all boron compounds is greater than 1ppmv.
2. according to the process of claim 1 wherein that the counterflow heat exchanger of being made by graphite using heats described initial action gas by the hot product gas that comprises trichlorosilane, HCl and unreacted initial action gas in described reactor.
3. according to the method for one of claim 1 to 2, wherein boron compound is introduced in described reactor together with hydrogen.
4. according to the method for one of claim 1 to 2, wherein boron compound is introduced in described reactor together with silicon tetrachloride.
5. according to the method for one of claim 1 to 2, wherein boron compound is introduced in described reactor together with hydrogen and silicon tetrachloride.
6. according to the method for claim 3 or claim 5, wherein in hydrogen, the concentration of all boron compounds is 4ppmv at least.
7. according to the method for claim 4 or claim 5, wherein in silicon tetrachloride, the concentration of all boron compounds is 4ppmw at least.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102012218741.3 | 2012-10-15 | ||
| DE201210218741 DE102012218741A1 (en) | 2012-10-15 | 2012-10-15 | Process for the hydrogenation of silicon tetrachloride in trichlorosilane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103723735A true CN103723735A (en) | 2014-04-16 |
Family
ID=49274521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310474431.7A Pending CN103723735A (en) | 2012-10-15 | 2013-10-12 | Process for hydrogenating silicon tetrachloride to trichlorosilane |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20140105805A1 (en) |
| EP (1) | EP2719664A1 (en) |
| JP (1) | JP5744993B2 (en) |
| KR (1) | KR101550497B1 (en) |
| CN (1) | CN103723735A (en) |
| CA (1) | CA2823590C (en) |
| DE (1) | DE102012218741A1 (en) |
| TW (1) | TWI498283B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109963645A (en) * | 2016-11-23 | 2019-07-02 | 瓦克化学股份公司 | Method for hydrogenization of silicon tetrachloride |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4536642A (en) * | 1980-06-27 | 1985-08-20 | Wacker-Chemitronic Gesellschaft Fur Elektronik-Grundstoffe M.B.H. | Device for treating gases at high temperatures |
| US6932954B2 (en) * | 2001-10-19 | 2005-08-23 | Tokuyama Corporation | Method for producing silicon |
| US20070073075A1 (en) * | 2005-09-29 | 2007-03-29 | Wacker Chemie Ag | Process and apparatus for the hydrogenation of chlorosilanes |
| CN101665254A (en) * | 2009-09-30 | 2010-03-10 | 洛阳世纪新源硅业科技有限公司 | Synthetic method of trichlorosilane |
| WO2011056959A2 (en) * | 2009-11-06 | 2011-05-12 | Gt Solar Incorporated | Systems and methods of producing trichlorosilane |
| WO2011102265A1 (en) * | 2010-02-18 | 2011-08-25 | 株式会社トクヤマ | Production method for trichlorosilane |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3455745A (en) | 1966-07-08 | 1969-07-15 | Dow Corning | Coating of objects with tetraboron silicide |
| US4340574A (en) * | 1980-08-28 | 1982-07-20 | Union Carbide Corporation | Process for the production of ultrahigh purity silane with recycle from separation columns |
| US4542004A (en) * | 1984-03-28 | 1985-09-17 | Solavolt International | Process for the hydrogenation of silicon tetrachloride |
| JP2710382B2 (en) * | 1989-01-25 | 1998-02-10 | 電気化学工業株式会社 | Method for producing high-purity dichlorosilane |
| DE19949936A1 (en) | 1999-10-16 | 2001-04-19 | Gerd Walter | Protection of construction parts of graphite and carbon materials on introduction into hydrogen atmosphere at above a specified temperature comprises mixing the hydrogen with an equal weight of methane |
| DE102005005044A1 (en) * | 2005-02-03 | 2006-08-10 | Consortium für elektrochemische Industrie GmbH | Process for the preparation of trichlorosilane by means of thermal hydrogenation of silicon tetrachloride |
| JP5205910B2 (en) | 2006-10-31 | 2013-06-05 | 三菱マテリアル株式会社 | Trichlorosilane production equipment |
| US20090060819A1 (en) | 2007-08-29 | 2009-03-05 | Bill Jr Jon M | Process for producing trichlorosilane |
| CN103228351B (en) * | 2010-09-27 | 2019-09-24 | Gtat公司 | Heating device and relative method |
| US20130121908A1 (en) * | 2010-10-01 | 2013-05-16 | Mitsubishi Materials Corporation | Method for producing trichlorosilane with reduced boron compound impurities |
| DE102011077970A1 (en) * | 2011-06-22 | 2012-12-27 | Wacker Chemie Ag | Apparatus and process for the temperature treatment of corrosive gases |
-
2012
- 2012-10-15 DE DE201210218741 patent/DE102012218741A1/en not_active Withdrawn
-
2013
- 2013-08-13 CA CA2823590A patent/CA2823590C/en not_active Expired - Fee Related
- 2013-08-27 TW TW102130587A patent/TWI498283B/en not_active IP Right Cessation
- 2013-09-17 JP JP2013192217A patent/JP5744993B2/en not_active Expired - Fee Related
- 2013-09-19 US US14/031,172 patent/US20140105805A1/en not_active Abandoned
- 2013-10-02 EP EP13187011.5A patent/EP2719664A1/en not_active Withdrawn
- 2013-10-12 CN CN201310474431.7A patent/CN103723735A/en active Pending
- 2013-10-15 KR KR1020130122536A patent/KR101550497B1/en not_active IP Right Cessation
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4536642A (en) * | 1980-06-27 | 1985-08-20 | Wacker-Chemitronic Gesellschaft Fur Elektronik-Grundstoffe M.B.H. | Device for treating gases at high temperatures |
| US6932954B2 (en) * | 2001-10-19 | 2005-08-23 | Tokuyama Corporation | Method for producing silicon |
| US20070073075A1 (en) * | 2005-09-29 | 2007-03-29 | Wacker Chemie Ag | Process and apparatus for the hydrogenation of chlorosilanes |
| CN101665254A (en) * | 2009-09-30 | 2010-03-10 | 洛阳世纪新源硅业科技有限公司 | Synthetic method of trichlorosilane |
| WO2011056959A2 (en) * | 2009-11-06 | 2011-05-12 | Gt Solar Incorporated | Systems and methods of producing trichlorosilane |
| WO2011102265A1 (en) * | 2010-02-18 | 2011-08-25 | 株式会社トクヤマ | Production method for trichlorosilane |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109963645A (en) * | 2016-11-23 | 2019-07-02 | 瓦克化学股份公司 | Method for hydrogenization of silicon tetrachloride |
Also Published As
| Publication number | Publication date |
|---|---|
| US20140105805A1 (en) | 2014-04-17 |
| TW201414675A (en) | 2014-04-16 |
| JP2014080357A (en) | 2014-05-08 |
| DE102012218741A1 (en) | 2014-04-17 |
| EP2719664A1 (en) | 2014-04-16 |
| KR101550497B1 (en) | 2015-09-04 |
| TWI498283B (en) | 2015-09-01 |
| KR20140048057A (en) | 2014-04-23 |
| CA2823590C (en) | 2015-10-13 |
| CA2823590A1 (en) | 2014-04-15 |
| JP5744993B2 (en) | 2015-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7442824B2 (en) | Process and apparatus for the hydrogenation of chlorosilanes | |
| CN100593513C (en) | Method for producing silicon | |
| CA2648378C (en) | Process for depositing polycrystalline silicon | |
| KR101037641B1 (en) | Recycling of high-boiling compounds within an integrated chlorosilane system | |
| US20170158516A1 (en) | Fluidized-bed reactor and process for preparing granular polycrystalline silicon | |
| CN101479193B (en) | Process for producing trichlorosilane and apparatus for producing trichlorosilane | |
| KR20110031284A (en) | Method for removing boron-containing impurities from halogen silanes and apparatus for performing said method | |
| TW200918452A (en) | Method for producing trichlorosilane, apparatus for producing trichlorosilane and method for producing polycrystal silicon | |
| KR101426099B1 (en) | Process for production of multicrystal silicon and facility for production of multicrystal silicon | |
| TW201643114A (en) | Process for workup of chlorosilanes or chlorosilane mixtures contaminated with carbon compounds | |
| KR101222303B1 (en) | Process for recycling high-boiling compounds within an integrated chlorosilane system | |
| KR20130005223A (en) | Process for producing polysilicon | |
| DE102011002436A1 (en) | Hydrogenation of organochlorosilanes and silicon tetrachloride | |
| CN102515871B (en) | Preparation method of carbon/carbon heater anti-scour C/SiC coating | |
| CN103723735A (en) | Process for hydrogenating silicon tetrachloride to trichlorosilane | |
| KR20130116311A (en) | Process and apparatus for conversion of silicon tetrachloride to trichlorosilane | |
| US20140124706A1 (en) | Process for preparing chlorosilanes by means of high-boiling chlorosilanes or chlorosilane-containing mixtures | |
| JP7020076B2 (en) | A method for manufacturing a reactant for manufacturing a polycrystalline silicon rod and a method for manufacturing a polycrystalline silicon rod using this reactor. | |
| TW201536798A (en) | Process for preparing trichlorosilane | |
| JP7477620B2 (en) | Method for removing impurities from chlorosilane mixtures | |
| JP7028604B2 (en) | Method for producing hexachlorodisilane | |
| CN104640810A (en) | Method for producing chlorosilanes by means of high-boiling chlorosilanes or chlorosilane-containing mixtures | |
| TWI853194B (en) | Process for removing an impurity from a chlorosilane mixture | |
| TWI472486B (en) | Process and plant for the purification of trichlorosilane and silicon tetrachloride | |
| JP2020500806A (en) | Method for hydrogenating silicon tetrachloride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140416 |